Brown chrome containing dyestuffs



United States Patent 2,711,404 V BROWN CHROME'CONTAINING'DYESTUFES Guido Schetty, Basel, Switzerland, assignor to 1. R.

Geigy A. G., Basel,.Switzerland,.a Swiss firm v a f 7N0 Drawing. Application December26, 1951,

" Serial No.263,507 a Claims priority, application Switzerland January 11, 1951' I 7 Claims. (C1. 26o '14sj.

It is known that mixtures of two metallisable dyestutfs 7' but-the az o dyestufisfl and II'may'not contain, any acid p I Patented-June 21, 1955 other substituen'tslsuch as hydrogen, chlorine, a methyl or an acylamin'o'group usual in "azo dyestuffs if desired,

[ groups, which would render them water soluble.

'As follows from paper. chromatograms andfraction;

, ,ated dyeings on wool, the chrome; containing "dyestuffs 1'5 of difierent constitution can be chromed in such a way' that complex chromium compounds resultwhich, in the same complex molecule contain both dyestutls bound.

to one and the same chrome atom. In thisway, mixed chromium complexes of metallisable azo dyestuffs which contain a sulphonic acid group have been described in the literature. "These/dyestuffs draw on to 'wool from a strongly acid bath. However, mixed chrome'complexes of metallisable dyestuifs which do not contain a sulphonic acid group and which can be used. as lacquer dyestuffs F are also known. All the processes for the production; of mixed chrome complex compounds of metallisable dyestuffs are concerned with combinations of those dyestuffs g which as complex chrome'compounds have the same or,

very similar shades, for instance combinations of navy blues and navy blues and blacks, of blackswith blacks,

or orange shades with reds.

It is surprising now to find that on chroming a mixture of equimolecular amounts of azo dyestuffs of the general Formula I (orange in the, form of, their chrome complexes) with azo dyestufis of the general Formula II (grey in the form of their chrome complexes):

OH OH X1-AN=N1L Z and OH OH X xN=N water soluble mixed chrome complex compounds are obtained which dye wool in brown shades.

In the above formulaez A and A represent aromaticvnuclei of the benzene series containing the hydroxy group in ortho position to the azo group and' the substituents X1 and X2 in'para position to the hydroxy group and wherein the oneX is a member selected from the class consistingof low molecular alkylsulphonyl and 7 groups andrthe other Xis a member selected 'from the" class of the nitro group, low molecular alkylsulphonyl and V low molecular alkyl and hydroxyalkyl groups, Pz'represents the radical of a 1-aryl-3-methyl-5-pyrazolone of the benzene series coupled in'the 4-position and Z means the radical of a 1-acylamino-7-hydroxynaphthalene con-- pled in the 8-position and the aromatic rings may contain above.

- The following may be listed asdiaZocomponents 'fdr the dyestuffs'of the general Formulae I and.- gusable ac cording to'. this invention: 2-aminophenol 4-me'thylphenol-4-sulphonic acid famide -rnethylamide, ethyl-' amide, -dimethylarnide, -diethy1'amide, oxethylarnide,

dioxethylamide, 6 chlo'ro 2 aminoph'enol-4-alkylf sulphones, I 6-acetylamino 2-amiiiophenolf4galltyl -sulphones j and '6 methyl-2-aminophenol-4 alkyl1sulphonesQ 6 -meth-- yl-, 6-acetylaminofand 6rchloroQ-aminophenol lsulphonic, acidamides'ete', 4-nitro-2-'aminophenol 6 chloroand 6-rnethyl-4-nitro-2-aminophenol, whereby; the dye-1 stuffs m'ade up from 2-amin'ophenol-4-alkyl "sulphones a have better drawing power from'a neutrallbathi {The drawing power on to woolfis' increased by,the entry of' a chlorine atom into the 6i-position ofthe Z a'mino henoI- 4-alky1su1phones, orthe' 2 amides.

- --The'followi'ng compoundsfor xafi p1e1ami dqae I, tion as' coupling componeritsl forfthe formation ofthe' dyestuffs of the general Formula 'I: l' phenyl-fa -methyl-i olone, l-(4-rnethoxyphenyl)J mefhYkEPYIaZoIone etc; Those pyrazolones which are substituted by halogen} drawing power from a neutral bathf'; I g

The following compounds for example come into quesatoms lead'to mixed complexes ,whichhave an'increased 11011 as coupling components for the formation of the dye:

stutfs of the general" Formula I I:, acetyl propionyl-, methoxyacetyh, carbomethoxyg "m'etlioxy-carbethoxyaminonaphthol-(l.7) etc. Here the increase'in'drawing from azo dyestuffs I and II which dyestuffs are'derived 9 from the same diazo components are technically of great advantage because they can be particularly easilyproduced by mixed coupling. followed by,chroming.- Par ticularly valuable combinations which fdraw well'from a ably'a methyl group, in'the acyl radical and on the other" neutral bath are obtained when -2p-aminophenol-4-alkyl sulphonesare used as diazo components in both dyestuif components 'and if on the one hand l-carbalkoxyarnino- 7-hydroxynaphthalenes with a low alkyl radical, preferwhereinA, A X, P2: and Z have'tlie rneanin iven j-aminophenol l-sulphonic acid hand 1-phenyl-3-methyl-5-pyrazolones chlorine substituted in the benzene ring are chosen as coupling components.

Normal and complex salts and hydroxides of trivalent chrome such as chrome acetate, chrome formiate, sodium chromosalicylate ammonium chromosalicylate are suitable as chroming agents. Chroming agents are particularly suitable which are capable of metallising in an alkaline or neutral medium such as the alkali salts of chromosalicylic acid. Chroming can be performed in the usual way, open or under pressure; in aqueous solution or suspension or in the presence of salts or inert organic solvents or solubility promoters. The chroming agents are used in such a way that at least I chrome atom corresponds to two molecules of metallisable azo dyestuff.

Apart from the valuable shade of the new complex chrome compounds which has never been attained before by mixed chroming of metallisable azo dyestuffs, the new dyestuffs according to this invention difier from the known mixed complexes by their high degree of afiinity to wool. Even from a neutral or weakly acid bath they give, according to the composition, strong and full wool dyeings. The dyeings are characterised by excellent fastness to light and by very good fastness to washing, milling and sea water. A particularly important advantage of the new mixed chrome complex compounds is that both the tips and the roots of the single hairs are evenly dyed.

In cases where the water solubility of the mixed chrome complex compounds according to the invention is not suflicient for the methods usual in textile dyeing, it can be improved by the admixture of alkali phosphates or carbonates or of wetting or dispersing agents.

The chrome containing azo dyestufis according to this invention are suitable not only for the dyeing of wool, but, due to their good drawing power from a neutral to weakly acid dye bath, are also suitable for the dyeing of silk and further for the dyeing of synthetic polyamide or polyurethane fibers such as nylon, Perlon or Lanital. They will also dye leather.

The behaviour of the mixed complexes according to this invention on dyeing is different from that of mechanical mixtures of the chrome complexes of the individual components. Mechanical mixtures have the disadvantage of producing dichroic dyeings on wool which does not occur with the mixed complexes.

The following examples illustrate the invention without limiting it in any way. Where not otherwise stated, parts are given as parts by weight and the temepratures are in degrees centigrade. The relationship of parts by weight to parts by volume is that of kilogrammes to litres.

Example 1 HOC SO2GHa OH OH HT SO2CH3 COOCH: II

18.7 parts of 2aminophenol-4-methyl sulphone are dissolved in 150 parts of water with 17 parts of cone. hydrochloric acid. The solution is cooled to 5 and, while adding ice at intervals, 6.9 parts of sodium nitrite 100% (as 33% solution) are added. On completion of the diazotisation, the reaction is made neutral by the addicarbonate. The diazo compound is poured at 03 into a solution of 22.8 parts of carbomethoxyaminonaphthol- 1.7) in 250 parts of water, 10.5 parts by volume of 10-n caustic soda lye and 15 parts of dehydrated sodium carbonate. The coupling is complete after a few hours. The whole is heated to the dyestuff which has partly entered into the solution is precipitated by the addition of sodium chloride and filtered otf (dyestuff II).

42.9 parts of the monosodium salt of dyestuff I and 43.7 parts of the monosodium salt of dyestutt II are stirred together in 2000 parts of water. 220 parts of a solution of ammonium chromo-salicylate (corresponding to 5.7 parts Cr) are then added and the whole is boiled for 5 hours. A brownish-black oil separates out which on cooling solidifies in crystalline form. Itis filtered off and dried. The new dyestutt is a dark powder which dissolves in hot water with a brown colour and dyes Wool from a neutral bath in deep brown shades. The dyeings have a very high degree of fastness to light and very good fastness to washing, milling and sea water.

A similar dyestuti is obtained if, for the production ofdyestufi I 18.7 parts of 2-aminophenol-4-methyl sulphone, 22.2 parts of 6-chloro-2-aminophenol-4-rnethyl sulphone or 20.2 parts of 6-methyl-2-aminophenol-4-methyl sulphone are used and instead of 22 parts of 1-(3'-chlorophenyl)-3-methyl-5-pyrazolone, 18.3 parts of 1phenyl-3- methyl-S-pyrazolone are used.

Example 2 SOs-CHs (LO-CH3 II 18.7 parts of 2-aminophenol-4-methyl sulphone are diazotised as described in Example 1. 8.7 parts of 1-pheny1-3-methyl-5-pyrazolone and 11 parts of acetylaminonaphthol-(1.7) are sprinkled into the still acid suspension of the diazonium compound. 35 parts by volume of 25% ammonia are then added and the whole is made up to 500 parts by volume and stirred at 03 until the mixed coupling is completed. This occurs after about 6 hours. parts of a solution of ammonium chromosalicylate (corresponding to 2.87 parts Cr) are then added, 400 parts of water are added and the whole is boiled for 10 hours. The dyestuff is precipitated as resin by the addition of sodium chloride. It is separated and dried. It is in the form of a dark powder which, after mixing with 10% of its weight of dehydrated sodium carbonate, has very good water solubility. The dyestuft dyes wool in dark brown shades-from a weakly acetic acid bath and the dyeings have very good 'fastness to light, washing a milling and their evenness is good. p 7 v r A very similar dyestuff is obtained if 18.8 parts of 2-aminophenol-4-sulphamide are used instead of 18.7

18.8 parts of 2-aminophenol-4-sulpharnide are dissolved in 150 parts of water with 17 parts of cone. hydro chloric acid. The solution is cooled to 5 and diazotised by the addition of 6.9 parts of sodium nitrite (as 33% solution). The-excess hydrochloric acid is neutralised by the addition of sodium hydrogen carbonate. The diazonium compound in the form of a neutral suspension is poured at 3 into a solution of 18.3 parts of l-phenyl-3- methyl-S-pyrazolone in 200 parts of water and parts of dehydrated sodium carbonate. been completed, the dyestufi is isolated. by filtration and. pasted with 37 parts of the monosodium salt of'dyestufi II in Example 1 in 2000 parts of water. 210 parts of a solution of ammonium chromo-salicylate (corresponding to After the coupling has what better from'a neu properties.

5.45 parts of Cr) are added and the. whole is'boiled for 4 hours. A black-brown solution is formed. Sodium chloride is added whereupon the mixed complexprecipitates. It is filtered oil and dried. The mixed complex'is a black powder which dyes wool from a weakly acetic acid bath in deep brown shades. The dyeings have very good fastness to light and good. wet fastness properties;

A dyestuff with somewhat better drawing power from a neutral bath but otherwise with similar propertiesis obtained if instead of 18.8 parts of 2-a n:1inophenol-.4 -sulpha-' mide, 22.3 parts of 6-chloro-2-aminophenol-4-sulphamide or 20.2 parts of 6-methyl-2-aminophenol-4-sulphamide are used or if instead of 18.3 parts of 1-phenyl-3-methyl- 5-pyrazolone, 23parts of 1-(4-nitrophenyl)3-methyl-5- pyrazolone are used. j

Example 4 so oHa is coupled with a solution dehydrated sodium carbonate. After heating to dyestuIiis-isolated -by filtration (dyestutf I).-

18.8 parts of .Z-aminophenol-4-sulphamide ariediazo-i I tis'ed according toExample 3,;stirred with'22.8fp'arts of carbomethoxyaminonaphthol-(1.7) "whereupon 35 parts by volume of'25% ammqnia are added at 2; The whole;

is stirredat 0-5 until the coupling has been completed and on the addition'of sodium ch 39.4 partsvof tlie'monosodium. salt "of 'dyestutf I and filtered 'off and dried. The new dyestufi, a black powder,

acid bath. The v (1 properties.

If, instead of 22.

or 27.4 parts of. carb omethoxyethoxy-arhinonaphthol- (1.7) are used, dyestuffs are obtained which draw some-itral bath but otherwise have similar a 3 parts of sodium'hydrogen carbonate.1,- 'The dia'zo .com-

' has disappeared. The mixture-ishcated'to the dye-,

1y precipitated .with sodium chloride and v -N="N I I HN i f ornm c iooonr H 18.7 parts of 2-aminophenol 4-methyl sulphone are diazotised according to Example 1 and neutralised with sodium hydrogen carbonate. This diazonium compound droxybenzenetrn propyl sulphoneareused and otherwise pound isthen'p'our'ed intoaksolutionf of 8f.'7 parts or; I l-p'henyl -3-methy15-pyrazolone;-1.1;4 parts of l-carbornethoxyamino-7-hydroxynaphthalene,. 4 parts of sodium hydroxide and 8 'parts of sodium;,carbonate in 300 parts of water and-coupled-at '0-5until the diaio compound stufiis complete filtered ofi. V V 1 V, I Pa s of ammonium chromo-alicylate (corresponding" to 2.85 parts, of Cr) are .added'to the dyestuif which as a paste has beenstirred in'to 1000 parts of water, and the whole is bOfledffOIflS hours under reflux. The brownblack; complex chrome compound is completely precipi- V tated with sodiumlchloride, drawn'oif by suction .and

dried. After thoroughlymixingwith 10% of its 'weight of sodium carbonate, the brown-black powder completely i dissolves in hot water 'with a brown colour. Itdyes}; s from a'neutral wool in'very level and fast brown shade bath containing ammonium sulphate.

If in the above'e'xample'instead' of 2-aminorl-hydroxy benzene-4-ethyl-sulphone;f 21.5 parts of 2-amino-1-hyat 18.3 parts of -1.-phe'riyl-'3 1 methyl-5-pyrazolone'in 200 parts of water and 20' parts of a loride the dyestu tfis; isolated by filtration (dyestufi II). 1

43;8'part's of the monosodiumsalt of dyestuff II are pasted; in 2000 parts of water, 240 parts of asolutionof ammo-1 nium chromo-salicylate (corresponding to 6.2 parts' of Cr) are added, and the whole is boiled .for 4 hours. A I dark brown solution is formed from which, bythe Iaddi-' tio'nof sodiumchloride, the'dyestutf is precipitated. Itis dyes Wool in very levelidark brown shades from an acetic yeingsl have very good :fa'stness to light 8 parts of carbomethoxyaminouaphthol-(1.'7) 24.3 parts of:carboethoxyaminonaphthol (1.7)

- TII: V

V :2 amino-lfhydroxybenzeneq ethyl F 111 7 j phone are dissolved in partsiof water 'andf17 parts'of conc. hydrochloric acid and diazotiz'ed at 0'5 withac'on-fv ,ce'ntrated' aqueous solution of 1.6.9 p'airts offsodium. nitrite. The excess mineral acid is then ueutralised 'with 20.1 parts of Z-amino-l-hydroxybenzene-4-ethyl sulphone are diazotized as described in Example 5 and then coupled with 17.4 parts of 1-phenyl-3-methyl-5-pyrazolone and 4 parts of sodium hydroxide in 500 parts of water at 10. The dyestuft is salted out in the usual way and drawn off under suction (dyestuff I).

18.8 parts of Z-amino-l-hydroxybenzene-4-su1phonic acid amide are diazotized in the same way as the diazo component in Example 5, and coupled at 5 with 20.1 parts of 1-acetylamino-7-hydroxynaphthalene dissolved in 500 parts of water and 4 parts of sodium hydroxide and 8 parts of sodium carbonate. The dyestufi is salted out and drawn off under suction (dyestufl II).

The united dyestuir" pastes are then stirred with 2000 parts of water and 250 parts of a solution of ammonium chromosalicylate (corresponding to 5.7 parts of chrome) and the whole is boiled for hours under reflux. The black-brown complex chrome compound which has already precipitated to a great extent is completely precipitated at 50 by means of common salt, drawn ofi under suction, dried and well mixed with of its weight of sodium carbonate. The dyestuif now completely dissolves in hot water with a brown colour and it dyes wool in very fast brown shades from a bath containing ammonium suiphate.

If instead of 2-amino-1-hydroxybenzene-4-ethyl sulphone, 21.6 parts of the corresponding 4-n-butyl sulphone are used for the production of dyestuff I, a very similar dyestufi is obtained.

Example 7 ()H i SOQNH? ()H HO OzCsHn COG-H3 II 18.8 parts of Z-amino-l-hydroxybenzene4-sulphonic acid amide are diazotized in a manner similar to the diazo component of Example 5 and coupled with 17.5 parts of 1-phenyl-3-methyl-5-pyrazolone dissolved in 500 partsof water with 4 parts of sodium hydroxide. The dyestufl is precipitated with common salt and drawn off under suction in the usual way. (Dyestuff I.)

23.0 parts of Z-amino-1-hydroxybenzene-4-n-amyl sulw phone are diazotized in a manner similar to the diazo component of Example 5 and coupled at 0S with 20.1 parts of 1-acetylamino-7-hydroxynaphthalene dissolved in 500 parts of water with 4 parts of sodium hydroxide and 8 parts of sodium carbonate. The dyestuif is salted out with common salt and drawn oil? under suction. (Dyestutf II.)

The unified dyestufi pastes are stirred with 2000 parts of hot water and then 250 parts of a solution of ammonium chromosalicylate, corresponding to 5.7 parts of chrome, are added and the whole is boiled for 5 hours under reflux. The black-brown chrome compound which has precipitated to a great extent is then completely precipitated at 50 with common salt, filtered off, dried and mixed with of its weight of sodium carbonate.

The dark brown powder so obtained dissolves well in hot water with a brown colour and it dyes wool in very fast brown shades from a bath containing ammonium sulphate.

If 20.9 parts of 1-( 3'-chlorophenyl)-3-methyl-5-pyrazo lone are used in the above example instead of l-phenyl- 3-methyl-5-pyrazolone, a very similar dyestufi is obtained.

Example 8 OrGHa 18.7 parts of 2-aminophenol-4-methyl sulphone are dissolved in 150 parts of water with 17 parts of cone. hydrochloric acid and diazotized at 5' in the usual way by the addition of 6.9 parts of sodium nitrite (as 33% 7 sodium hydrogen carbonate and then poured into a solution of 22.8 parts of carbomethoxyaminonaphthol-(1.7) in 250 parts of water, 10.5 parts by volume of 10-n caustic soda lye and 15 parts of dehydrated sodium carbonate. The coupling is complete after some hours (dyestufi H).

N0; COOCH: II.

On completion of the diazotisation, the whole is made exactly neutral to Congo red by the addition of On completion of the coupling, the suspension ofdyestuff I is poured into that of dyestuft II. The two dyestufis are boiled together for some hours with a solution of ammonium chromosalicylate (corresponding to 5.7 parts of Cr). The dyestufi is then filtered off and dried. The new dyestufi is in the form of a black powder which dissolves in hot water with a brown colour. It dyes wool in very full deep brownshadesfrom aneutr'al or weakly acid bath. The dyeings have very good fastness to washing, milling, sea water and stoving.

Similar dyestuffs are obtained if instead of 18.7.parts of Z-aminophenol 4 methyl sulphone, 18.8 parts of 2-aminophenol-4-sulphamide or 23.2 parts of Z-aminophenol-4-sulphethanolamide are used for the production of dyestuff I.

Example 9 few hours (dyestuft 11) I I I V p I On completion of the coupling thesuspension of dye- I stufl I ispoured into thatof dyestuft II. The two dy e f 15.4 parts of 4-n1tro-2-am1nophenol are dlaZOtlZfid as ismfis are ed? toget a solution of ammonium described in Example 8. The diazoniurn solution, neutralised with sodium hydrogen carbonate, is poured into a solution of 22 parts of 1-(3'-chlorophenyl)-3-methyl-5- pyrazolone in 300 parts of water and 16 parts of dehydrated sodium carbonate. The coupling is complete'after 7 yestufi is precipitatedand isolated some hours and the in the usual way (dyestufiI) r 18.7 parts of 2-aminophenol-4-methyl sulphone arediazotised as described in Example 8 and neutralised by the addition of sodium hydrogen carbonatefThedi 18.7 parts of -2'-aminophenol-'4- methyl sulphonie are diazotised in the jusualiway. (The diazonium compound; isneutralised withsodiurn hydrogen-carbonate and poured into .a solution of 221 parts of 1-(3'- chlorophenyl)-3- methyl-5-pyrazolone in 300. parts of water and 16 parts of j Z dehydrated sodium carbonate -(dye'stuif I) 5 24.4 partsof.2-aminophenol-4 sulphodiethylamide are dissolved in l50;part's of water" with 1 0.5 parts by volume 6 of .IO-n caustic soda lye, 6.9 parts of sodium nitrite-100% f U (as 33% solution) are added and" the whole is poured slowly at 0.5 into a solutionof 25 parts offconc. hydro-' chloric acid and an equal amount of water." The diazonium compound in the. form of. suspension is made 3 exactly neutral with sodium hydrogenca rbonate and'then poured into a solution'of 22.8 parts ofcarbornethoxyaminonaphthol- (-1.7 in 250 parts of water, 10.5 parts by volumeof 10'n"cau'stic soda lye and parts of dehydrated sodium carbonate; he dy'estuif is formedafter a v chromo-salicylate-"(corresponding 'to; 5.7' parts Cr) is 5- added and the'ivholeisboiled for some hours. The dyestufi -is precipitated in theforirj of resin by the addition of sodium chloride. It is fse paratedand dried. It is a black powder which dissolves Qwell iniwater' and dyeswool azonium compound is poured into 'asolution of 22.8

parts of, carbomethoxyaminonaphthol-(1.7)--in' 250 parts of water, 10.5 parts by volume of caustic soda ly e IO-n and 15 parts of dehydrated sodium carbonate. The coupling is complete after some hours. The whole is heated to the dyestutI, which has partly gone into solution, v

is precipitated by theaddition of sodium chloride and filteredoif. (Dyestufl II.) a Y 43.7 parts of dyestufi II and 39.6 parts of, dyestufi I are pasted together in 2000 parts .of water and, with a solution of ammonium chromo-salicylate (corresponding to 5.7 parts Cr) are boiled for some hours The dyestufi so formed is filtered off and dried.

Mixed with 30% of its weight of sodium carbonate, the j new dyestufl is a black powder which dissolves inhot i 5 water with a brown colour. It dyes wool in deep brown shades from a neutral or weakly-acid bath. The dyeings have very good fastness to light, washing, milling, sea water and stoving.

A similar 'dyestufi is obtained if instead of 18.7 parts I of Z-arninophenol 4 methyl sulphone, 21.6 parts of 2-aminopl1enol-4-sulphodimethylamide are 'used' for the production of dyestufi II.

18 .8 parts 'of 2-aminophenol-4-sulphamide' are dissolved in 150. parts of =Water-with17; parts of cone.

hydrochloric acid. The solution is cooled to 5?, and y diazotised by the addition of 6.9 parts of sodium nitrite (as 30% solution). The excess hydrochloric acid is neutralised by the addition of sodium hydrogen carbonate. The diazonium compound in the form of a neutral paste is poured at 3 into a solution of 22 parts of 1-(3-chlorophenyl)-3-n1ethyl 5-pyrazolone in 300 parts of water and 16 parts of dehydrated sodium carbonate (dyestuif I).

24.4 parts of 2-aminophenol-4-sulphodiethylamide are diazotised as described in Example and neutralised with sodium hydrogen carbonate and coupled with a solution of 22.8 parts of carbomethoxyaminonaphthol- (1.7) in 250 parts of water, 10.5 parts by volume of 10n caustic soda lyeand parts of dehydrated sodium carbonate (dyestutf II).

On completion of the coupling, the two dyestufi suspensions are stirred together, a solution of ammonium chromo-salicylate (corresponding to- 5.7 parts CI) is added and the whole is boiled for some hours. The dyestuff is precipitated in the form of resin by the addition of sodium chloride. It is filtered and dried. It is a black powder which dissolves Well in hot water and dyes wool in deep brown shades from a weakly acid bath. The dyeings are very full and have good fastness to Washing, milling and sea water and stoving.

Example 12 23.2 parts of 2-aminophenol-4-sulphethanolamide are dissolved in 150 parts of water with 17 parts'of conc. hydrochloric acid and diazotised by the addition of 6.9 parts of sodium nitrite (as 30% solution). On completion of the diazotisation, the excess hydrochloric acid is neutralised with sodium hydrogen carbonate and the diazonium compound is coupled with a solution of 22 parts of 1-(3'-chlorophenyl)-3-methyl-5-pyrazolone in 300 parts of water with 16 parts of dehydrated sodium carbonate (dyestulf I).

24.4 parts of 2-amino-4-sulphodiethylamide are diazotised as described in Example 10 and the excess hydrochloric acid is neutralised with sodium hydrogen carbonate. This neutral diazonium paste is coupled with a solution of 22.8 parts of carbomethoxyaminonaphthol- (1.7) in 250 parts of water, 10.5 parts by volume of 10-n soda lye and 15 parts of dehydrated sodium carbonate (dyestult II).

The two dyestuft suspensions are stirred together, a solution of ammonium chromo-salicylate (corresponding to 5.7 parts Cr) is added and the Whole is boiled for some hours. The dyestuff is precipitated in the form of resin by the addition of sodium chloride. It is filtered and dried. It is a black powder which dissolves well in hot water and dyes wool in brown shades from a weakly acid bath. The dyeings are very level and full and have excellent fastness to washing, milling sea. Water-and stoving.

i 2 Example 13 COOCHa 24.4 parts of 2-aminophenol-4-sulphodiethy1amide are diazotised and after being neutralised with sodium hydrogen carbonate are poured into a solution of 13 parts of carbomethoxyaminonaphthol-(1.7), 12 parts by volume of 10-n caustic soda lye, 9.3 parts of 1-(3- chlorophenyl)3-methyl-5-pyrazolone and 15 parts of dehydrated sodium carbonate in 1000 parts of water.

On completion of the coupling, a solution of ammonium chromo-salicylate (corresponding to 2.85 parts Cr) is added to the suspension of the dyestuffs formed and the whole is boiled for some hours. A dark brown solution is formed to which sodium chloride is added. The dyestufi? precipitates in the form .of resin. It is separated and dried. It is in the form of a dark powder which, after mixing with 20% ofv its weight of dehydrated sodium carbonate, dissolves well in water. It dyes Wool in brown shades from a weakly acid bath. The dyeings have very good fastness to milling, Washing and light.

Similar dyestufis are obtained if instead of 24.4 parts of 2-aminophenol-4-sulphodiethylamide, 23.3 parts of 2-aminophenol-4-sulphethanolamide or 27.6 parts of 2- aminophenol-4-sulphodiethanolamide are used.

stirred until there is no longer any trace of the diazo compound and then heated to 70 parts of common salt are added and the dyestuft is filtered oil (dyestuill).

.7 parts of cone. hydrochloric acid are added-to 300- parts of a solution which contains 24.4 parts of fi-acetylamino-Z-arnino-1-phenol-4-methyl sulphone in the .form

of the chlorohydrate. After cooling to f3,'a solution containing 6.9 parts of sodium nitrite is added; The

diazonium compound which has. partly precipitated in the form of. clay yellow coloured crystals is neutralised' with sodium hydrogen carbonate and then poured into a solution of 23 parts of carbomethoxyaminonaphthol- 1.7) in 200 parts of water, 4.2parts of sodium hydroxide and 15 parts of dehydrated sodium carbonate. whole is stirred at -5 until the dyestuif has completely formed. The dyestutf is then completely precipitated by the addition of common salt and filtered ofl? (dyestutf H).

48.6 parts of the monosodium salt'oftdyestufi I and 49.4 parts of the monosodium salt of dyestuif' II' are phone is acetylated to 6-nitro-2-acetylamino-1-phenol-4- methyl sulphone. This is dissolved with diluted caustic soda lye and reduced catalytically and the 6-nitro-2- acetylamino-l-phenol-4-methyl sulphone is precipitated with acetic acid. Recrystallised from hot water, white needles are obtained. M. P. 191-192.

Similar dyestuffs are obtained if, instead of 24.4 parts of 6-acetylamino-2-amino-l-phenol-4-methyl sulphone, 26.0 parts of 6-carbomethoxyamino-2-amino-1-phenol-4- methyl sulphone or 27.4 parts of 6-carbethoXyamino-2 amino-1-phenol-4-methyl sulphone are used.

Example V 2 parts of the dyestuff obtained according to Example 1 are dissolved in .4000 parts 'of'water, 10 parts of Glaubers salt are added and 100, parts of wool are entered at 50. The bath is brought to the boil within 30 minutes and held at the boil for 1 /2 hours while moving the wool well. Thereafter the goods are rinsed and dried. The wool which has been dyed in a deep brown shade is very fast to milling, alkali, sea water, and light. The dyeing is also characterised fastness to rubbing and carbonisingr What I claim is: 7

l. A complex chromium compound of the general formula I-Cr-II, wherein I and -II are co-ordinated is obtained as follows: 6-nitro-2-aminophenol-4-methyl sul-.

Thej' Z represents the radical lof-a 1-acylamino-.'7.-hydroxynaph{ by good I monoazo dyestuffs freeifrom carboxylic and sulphonic acid groups of the formulae:

en 0H 7 7 en s OH X --AN=Nl z and. XgA-N=N- wherein A and A represent aromaticflnuclei of, the a benzene series containing the hydroxy'grou'p in ortho position to the azo group and the substitu'en'tsXr and X2 in para position to the hydroxy group and wherein the one X is a member selected from the class consisting of low molecular alkylsulphonyl and I-Cr-II'Wherein, I and II groups and the other X is a member selected from the and class of the nitro group, low molecular .alkylsulphonyl -.sents the radical of a 1-aryl-3methyl-5-pyrazolone of the benzeneseries' coupled in 4-position and Zrrepresents the radical of a -1-acylamino-7-hydroxynaphthalene coupled in 8 -position;

2. A complex chromium compound of the general formula I-Cr- II whereinfliandll are co-ordinated monoazo dye'stuffsifree fromfsulphonic. and carbo xylici 7 'acid groups oftheformulaez' I t wherein Ri'and R2 represent membersselected fromthe class 'c'on sisting of hydrogen, chlorine, methyl and acylamino groups, 7 V V i R3 represents, a lowqmolecular aliphatic hydrocarbon radical, 1

lone of the benzene series coupled in4-positionjandq thalene coupledin 8-position. V

3..A complex chromium compound of theiformula -I 'Cr-II-.wh'erein land (II are co -ordinated mo'ndazo J dyestuffs of the formulae:

BQ zN(C 2H5)I V chromium compound of the formula 4. A 'c omplex' dyestuffs of the formulae:

1 V I v V N'=N--o+ o-om d1 a v V (I) 7 on no sol-on; @6003. H

Pz represents theradical 'of a l-aryl 3-methyl-5-pyrazoare co-ordinated monoazo 15 16 5. A complex chromium compound of the .formula 7. A complex chromium compound of the formula ICrII wherein I and II are co-ordinated monoazo ICr-II wherein I and H are co-ordinated monoazo dyestufis of the following formulae: dyestuffs of the formulae:

OH DE I N=NO--OCH; N=NC-CCHa 110i ii HO-g LL N N SOPCHS 02-0113 ()H H0 (E E0 V =N N=N 7 l HN- HN- SOz-CH: GOOCHa (II) SOQ-OHz C0-CH3 6. A complex chromium compound of the formula 1 IC1-II wherein I and II are co-ordinated monoazo References Cited In the file 0f fills Patel!t dyestuffs ofthe formula if UNITED STATES PATENTS 2,104,357 Straub et a1 Jan. 4, 1938 2,551,056 Schetty May 1, 1951 N=NO(!3CHa V HO-G 1.

Oil-CH3 OH HO 7 SO2GHa COOCH: (II) 

1. COMPLEX CHROMIUM COMPOUND OF THE GENERAL FORMULA I-CR-II, WHEREIN I AND II ARE CO-ORDINATED MONOAZO DYESTUFFS FREE FROM CARBOXYLIC AND SULPHONIC ACID GROUPS OF THE FORMULAE: 